Functional zirconium phosphate nanosheets enabled transfer hydrogenolysis of aromatic ether bonds over a low usage of Ru nanocatalysts

Catalytic hydrogenolysis of aromatic ether bonds is a highly promising strategy for upgrading lignin into small-molecule chemicals,which relies on developing innovative heterogeneous catalysts with high activity.Herein,we designed porous zirconium phosphate nanosheet-supported Ru nanocatalysts(Ru/ZrPsheet)as the heterogeneous catalyst by a process combining ball milling and molten-salt(KNO_(3)).Very interestingly,the fabricated Ru/ZrPsheetshowed good catalytic performance on the transfer hydrogenolysis of various types of aromatic ether bonds contained in lignin,i.e.,4-O-5,a-O-4,β-O-4,and aryl-O-CH3,over a low Ru usage(<0.5 mol%)without using any acidic/basic additive.Detailed investigations indicated that the properties of Ru and the support were indispensable.The excellent activity of Ru/ZZrPsheetoriginated from the strong acidity and basicity of ZrPsheetand the higher electron density of metallic Ru0as well as the nanosheet structure of ZrPsheet.

Incorporation of Nano-Zinc Oxide in Lamellar Zirconium Phosphate: Synthesis and Characterization

In order to provide ultraviolet barrier, antifungal and antibacterial properties, nano-zinc oxide (ZnO) was added to lamellar zirconium phosphate (ZrP). The phosphate was synthesized via reaction of zirconium oxychloride octahydrate and phosphoric acid following its chemical modification with Jeffamine and nano-ZnO. Diffractometric, morphological, thermal, structural and relaxometric evaluations were conducted. Fourier transform infrared spectroscopy (FTIR) revealed increase of the area between 4000 - 3000 cm-1 due to the formation of ionic specie PO? +NH3-[C-(H)(CH3)-CH2-O-(C-(H)(CH3)-CH2-O)8-(CH2-CH2-O-CH3)] and nano-ZnO particles. Wide-angle X-ray diffraction indicated that intercalation of Jeffamine was successful. Thermogravimetry confirmed that nano-ZnO particle forced the expulsion of Jeffamine outside ZrP galleries. Scanning electron microscopy evidenced the Jeffamine intercalation and sample heterogeneity. Hydrogen molecular relaxation indicated the increase of molecular rigidity owing to the formation of ionic specie and the addition of nano-ZnO particles. It was postulated that a multifunctional and miscellaneous material constituted by as prepared ZrP, some delaminated ZrP platelets and nano-ZnO particles was achieved. The material has potential for usage as filler in polymeric composites.

Preintercalation of Layered γ-Zirconium Phosphate for Preparation of Immobilized Hemoglobin

Layeredγ-Zirconium phosphate (γ-ZrP) preintercalated with butylamine, tetra (n-butylammonium)hydroxide, dimethylamine respectively, or only ultrasonificated, for preparation of immobilized hemoglobin were investigated in this report.

Antimicrobial effects of silver zeolite,silver zirconium phosphate silicate and silver zirconium phosphate against oral microorganisms

Objective:To evaluate the antimicrobial activities of silver inorganic materials,including silver zeolite(AgZ),silver zirconium phosphate silicate(AgZrPSi)and silver zirconium phosphate(AgZrp),against oral microorganisms.In line with this objective,the morphology and structure of each type of silver based powders were also investigated.Methods:The antimicrobial activities of AgZ,AgZrPSi and AgZrP were tested against Streptococcus mutans,Lactobacillus casei,Candida albicans and Staphylococcus aureus using disk diffusion assay as a screening test.The minimum inhibitory concentration(MIC)and minimum lethal concentration(MLC)were determined using the modified membrane method.Scanning electron microscope and X-ray diffraction were used to investigate the morphology and structure of these silver materials.Results:All forms of silver inorganic materials could inhibit the growth of all test microorganisms.The MIC of AgZ,AgZrPSi and AgZrP was 10.0 g/L whereas MLC ranged between 10.0-60.0 g/L.In terms of morphology and structure.AgZrPSi and AgZrP had smaller sized particles(1.5-3.0μm)and more uniformly shaped than AgZ.Conclusions:Silver inorganic materials in the form of AgZ,AgZrPSi and AgZrP had antimicrobial effects against all test oral microorganisms and those activities may be influenced by the crystal structure of carriers.These results suggest that these silver materials may be useful metals applied to oral hygiene products to provide antimicrobial activity against oral infection.

Tribological Properties of Magnesium Ion-exchanged α-Zirconium Phosphate as a Solid Lubricant Additive in Lithium Grease

Magnesium ion-exchanged a-zirconium phosphates(Mg-α-ZrP) with particle sizes of 600 and 80 nm were prepared through the sealed ion-exchange and one-step hydrothermal synthesis methods, respectively. It was found that larger particles of Mg-α-ZrP had a higher load-carrying capacity than that of smaller particles, whereas smaller Mg-α-ZrP particles had better anti-wear properties than that of larger Mg-α-ZrP particles under mild loads. The correlation between the particle size of the sample and the surface roughness of the friction pair thus seems to be a key factor influencing the performance.

α-ZrP层状纳米片的插层制备及其摩擦学性能研究

以层状α-Zr(HPO_(4))_(2)·H_(2)O(α-ZrP)为前驱体,采用间接插层法合成十二烷基三甲基溴化铵(DTAB)插层DTAB-ZrP材料,利用XRD和电镜分析手段对DTAB-ZrP晶体结构和形貌进行表征,采用FT-IR、TGA和CHN元素分析仪对DTAB-ZrP样品的有机物基团和有机物含量进行分析。采用流变仪和四球摩擦磨损试验机研究固体添加剂DTAB-ZrP对锂基脂流变性能和摩擦学性能的影响,借助3D光学表面轮廓仪、扫描电子显微镜和X射线能量色谱仪对摩擦副表面的磨痕进行表征分析。结果表明:DTAB-ZrP样品具有良好的结晶度,作为锂基脂固体添加剂改善了基础脂的黏弹性和黏温性能;在不同载荷和长时间运行下,含DTAB-ZrP锂基脂均表现出优异的承载力、减摩和抗磨性能。磨损表面化学元素分析显示,在摩擦过程中DTAB-ZrP在摩擦副表面形成了物理保护膜。

Synthesis and Tribological Properties of Sodium-Ion-Exchangedα-Zirconium Phosphate

Sodium-ion-exchangedα-zirconium phosphate(Na-α-ZrP)was synthesized by using disodium hydrogen phosphate as the sodium source,which was an efficient ion exchange way.The tribological properties of Na-α-ZrP as an additive in lithium grease were investigated by a four-ball friction tester and a SRV tester,respectively.The synergistic effect of Na-α-ZrP with ZDDP was also studied.Results indicate that Na-α-ZrP can effectively improve the antiwear and friction-reducing properties of lithium grease.Combined with ZDDP,the grease demonstrated excellent anti-wear performance,especially under high loads.The possible wear mechanism was discussed by observing the worn surface using 3D optical profiler,scanning electron microscopy(SEM),energy-dispersive spectrometry(EDS),and X-ray photoelectron spectroscopy(XPS).The simple synthetic method and superior tribological performance make the Na-α-ZrP become a potential choice for lubricant additives.

Direct Conversion of Glucose to 5-Hydroxymethylfurfural over Zirconium Phosphate Catalyst in a Biphasic System

Efficient and selective production of 5-hydroxymethylfurfural(HMF) from glucose was achieved in the presence of zirconium phosphate(ZrPO) catalyst in a biphasic system.With the use of this catalyst,a high HMF yield of 56.8% was obtained from glucose in a water-tetrahydrofuran(THF) biphasic system.Characterization results showed that such catalyst had weak to strong acid sites and contained both Lewis and Br?nsted acid sites.The results of comparative experiments over some other solid acid catalysts demonstrated that the Lewis acid sites on the ZrPO catalyst played a crucial role in the isomerization of glucose to fructose and the Br?nsted ones were active in the dehydration of generated fructose to HMF.Moreover,less levulinic acid(LA) and formic acid(FA)(0.5%) were detected in the reaction solution,indicating that this ZrPO catalyst exhibited high selectivity towards the formation of HMF.Furthermore,the ZrPO catalyst was very stable and could maintain its activity after being used for six times.

A new method of immobilizing ionic liquids into layered zirconium phosphates

In this work, a new method of a series of ion liquids (ILs) 1-alkyl-3-methylimidazolium chloride [Cnmim]Cl (n = 2, 4, 6, 8) intercalation into layered zirconium phosphates was investigated. It was found that the α-ZrP·2BA (i.e. pre-intercalated BA was arranged in a bilayer mode in the galleries of α-ZrP) was a suitable host for intercalation ILs: ILs was inserted through exchanging pre-intercalated BA. And the intercalation orientation was investigated by use of X-ray diffraction (XRD) experiments and molecular modeling calculation.

Synthesis,Proton Conductivity and Humidity Sensing Property ofγ-Type Zirconium Hydrogen Phosphate,Zr(HPO_4)_2·2H_2O

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Fluorescence property of tris(2,2′-bipyridine)ruthenium(Ⅱ)dichloride immobilized in the gallery ofγ-zirconium phosphates

Tris （2, 2′-bipyridine） ruthenium （Ⅱ） （Ru（bpy）3^2＋） dichloride was successfully immobilized into the galleria of layered gamma zirconium phosphate （γ-ZrP） preintercalated by butyl amine（BA）. The compounds showed extended luminescence lifetime of about four times of unimmobilized metal complex.

In Vitro Cytotoxicity Evaluation of Highly Absorbent Foam Dressings Based on Silver Zirconium Phosphate via IC50 Value

In this study, we, for the first time, tried to apply IC50 values (inhibitory concentration estimated to affect the endpoint in question by 50%) in the MTT colorimetric assay to investigate the cytotoxic effects of highly absorbent foam dressings based on silver zirconium phosphate, a newly nano-based matrix. Our results showed that silver released from dressings based on silver zirconium phosphate attributed mainly to highly cytotoxic to L929 cells cultured with MEM containing 10% fetal bovine serum. In addition, we have also compared the IC50 values among different dilutions of AgNO3 solution, silver based dressing extracts and material reference control (ZDEC) extracts using the optimized MTT assay, along with characterizing the silver content in the dressing extracts using atomic absorption spectroscopy. Results have shown that the IC50 values of AgNO50 solution, silver based dressing extracts and ZDEC extracts are 3.5 μg/mL, 3.8 μg/mL and 8.4%, respectively. And there exist some good agreements between qualitative and quantitative evaluation method as well. In conclusion, our study has led to the view that the IC50 value is a promising quantitative index for screening cytotoxicity with regard to silver based dressings.

SYNTHESIS, CHARACTERIZATION AND APPLICATION IN PEMFC OF ZIRCONIUM OXO PHOSPHATE-SULFATE

Mesoporous zirconium oxo phosphate-sulfate was synthesized by hydrothermal method with hexadecyltrithylammonium bromide(CTAB)as the template and with zirconium nitrate or zirconium oxychloride as zirconium source.The optimum two-stage process was established, ^(31)P MAS NMR showed that the states of phosphate species were changed with further postsynthesis treatment by sulfate acid. The transformations of the structures at different temperatures from room temperature to 1173 K were investigated by XRD. ...

Study on Synthesis and Intercalation Behavior of Layered Zirconium Proline-N-methylphosphonate-phosphate

Zirconium proline-N-methylphosphonate-phosphate (α-ZPMPP) was prepared in the presence of HF for the first time. The a-ZPMPP sample is highly crystallized with interlayer distance of 1.52 nm. The interlayer distance of complex of α-ZPMPP with n-butylamine (α-ZPMPP-BA) is in 0.45 nm larger than that of α-ZPMPP. The α-ZPMPP possesses different intercalation behavior of host-guest compound from α-ZP.

New insight into polystyrene ion exchange resin for efficient cesium sequestration:The synergistic role of confined zirconium phosphate nanocrystalline

Polystyrene resins(PS)have been practical ion exchangers for radionuclides removal from water.However,nonspecific effects of ion exchange groups continue to be a major obstacle for emergency treatment with coexisting ions of high concentrations.The selectivity for Cs+enables zirconium phosphate(ZrP)to be the most promising inorganic sorbent for radioactive cesium extraction,despite being difficult to synthesize and causing excessive pressure loss in fixed-bed reactors due to fine powder.Herein,through facile confined crystallization in host macropores,we prepared PS confinedα-ZrP nanocrystalline(ZrP-PS).Size-screen sorption of layeredα-ZrP and sulfonic acid group preconcentration of PS synergistically enable a considerably higher Cs+affinity of ZrP-PS than PS,as confirmed by X-ray photoelectron spectroscopy(XPS)analysis.ZrP-PS demonstrated remarkable cesium sequestration performance in both batch and continuous experiments,with a high adsorption capacity of 269.58 mg/g,a rapid equilibrium within 80 min,and a continuous effluent volume of 2300 L/kg sorbents.Given the excellent selectivity for Cs+and flexibility to separate from treated water,ZrP-PS holds great promise as purification packages for the emergency treatment of radioactively contaminated water.

Pa-APP/PER/α-ZrP阻燃聚丙烯酸酯乳液的制备及性能

首先,采用乳液聚合法制备了固含量为45%的水性聚丙烯酸酯乳液,随后向其中加入复合阻燃剂哌嗪改性聚磷酸铵(Pa-APP)、季戊四醇(PER)和α-磷酸锆(α-ZrP)制备了Pa-APP/PER/α-ZrP阻燃聚丙烯酸酯乳液,并测定其阻燃效率,分析其阻燃机制。通过正交实验得到复合阻燃体系的最佳配方为:复合阻燃剂在聚丙烯酸酯乳液中添加量为25%(以聚丙烯酸酯乳液固体质量计,下同),其中α-ZrP添加量为2%(以聚丙烯酸酯乳液固体质量计,下同),m(Pa-APP)∶m(PER)=4.5∶1,在该条件下制备的Pa-APP/PER/α-ZrP阻燃聚丙烯酸酯乳液的极限氧指数达30.4%,UL-94测试达V-1等级,热释放速率峰值和总热释放量比纯聚丙烯酸酯分别降低了77.65%和39.73%。通过SEM-EDS、XPS、FTIR表征了Pa-APP/PER/α-ZrP阻燃聚丙烯酸酯乳液燃烧后的残炭形貌和成分。结果表明,Pa-APP/PER/α-ZrP阻燃聚丙烯酸酯乳液能够有效抑制聚丙烯酸酯燃烧过程中的熔滴,提高残炭量并改善炭层结构,降低燃烧过程中的总产烟量,从而提高Pa-APP/PER/α-ZrP阻燃聚丙烯酸酯乳液的阻燃安全性能。

锆钇废料制备氧化钇和磷酸锆吸附剂及其性能评价

钇稳定氧化锆是一种性能优异的材料,在其生产和使用过程中会产生大量切削边角料等固体废物,对其进行回收处理,有助于环境保护和资源有效利用。由于废料性质稳定,将其回收和转化为有价值的产品成为资源有效利用的关键。研究提出将锆钇废料转为氢氧化锆和草酸钇中间体,并进一步转化为磷酸锆和氧化钇吸附剂,增加锆钇废料资源化新路线。该合成路线以乙醇为分散助剂,氢氧化锆、草酸和磷酸二氢钠按物质的量为1∶2∶2比例混合,373 K反应6 h制得层状磷酸锆对钾离子的吸附容量为151.6 mg/g,可将模拟高钾血清中的钾浓度降至人体正常水平(4.51 mmol/L)且不损失过多的钠离子。以草酸钇氨水合物煅烧得到的氧化钇,可作为硫酸根的高效吸附剂。研究结果显示,在1073 K煅烧草酸钇氨水合物得到的氧化钇,在添加量为10 g/L、强酸性溶液的条件下,可保持98.6%的硫酸根去除率。硫酸根离子被氧化钇吸附的过程遵循Langmuir等温吸附模型,属于单分子层吸附,其准二级动力学常数为2.03×10^(-3) g/(min·mg),属于化学吸附。

锆离子作用下镀锌板刷涂磷化-皂化工艺及膜层性能

[目的]对于一些应用于特殊场合的镀锌板,在磷化后还要进行皂化处理,以满足摩擦因数低及耐蚀性优良的使用要求。[方法]采用刷涂的方式对镀锌板磷化处理后再皂化。对比了镀锌板经不同工艺处理后的表面微观形貌、动摩擦因数和耐蚀性。研究了刷涂磷化液中添加不同质量浓度(0~20 g/L)的锆盐时对磷化-皂化膜层表面微观形貌和动摩擦因数的影响。[结果]皂化处理可提高磷化膜表面的平整性和均匀性,降低磷化膜的动摩擦因数,但对磷化膜水接触角的影响很小。磷化液中添加锆盐可以有效降低磷化-皂化膜层的动摩擦因数,令其满足动摩擦因数小于0.16的应用要求。[结论]通过刷涂方式可在镀锌板表面获得动摩擦因素低、耐蚀性好的磷化-皂化膜,有望实现工程化应用。

高度取向磷酸锆/环氧树脂纳米复合涂层的防腐蚀性能

针对金属防腐蚀的需求,采用简单的喷涂法在金属基底上制备了高度取向磷酸锆/环氧树脂纳米复合涂层。利用透射电镜和X射线衍射分析探究了复合涂层中磷酸锆纳米粒子的分散形貌,采用电化学交流阻抗谱和动电位极化曲线等测试评价了复合涂层的防腐蚀性能和其作用机理。结果表明,高度取向的磷酸锆纳米粒子可有效地增加水、氧气、电解液的扩散路径,改善涂层的防腐蚀性能。此外,该绝缘涂层也可进一步阻止腐蚀介质的迁移,增加涂层电阻,显著提高环氧树脂涂层对金属基底的长期防护性能。

有机胺插层α-ZrP复合材料的研究

层状纳米复合材料因具有常规复合材料所没有的结构、形态及较常规复合材料更优异的性能而引起人们的广泛关注。α-磷酸锆(α-Zr(HPO4)2·H2O,简写为α-ZrP)作为一种合成的层状无机物,其离子交换容量(600 mmol/100 g)是粘土的6倍,并具有长径比可控和粒子尺寸分布较窄等特点,是制备聚合物/层状无机物纳米复合材料的优良基体。采用HF络合法制得α-ZrP微晶,再运用直接插入法分别将正丙胺、正丁胺、正己胺和正辛胺插入α-ZrP,制备了α-ZrP和烷基胺的插层复合材料,并通过X射线衍射(XRD)及电子扫描电镜(SEM)对材料的结构和形貌进行表征。